3-hydroxy-p-dioxane-2-methanol

ABSTRACT

A novel compound represented by the formula   IS USEFUL AS AN INTERMEDIATE FOR PREPARATION OF SEQUESTRANT COMPOUNDS REPRESENTED BY THE FORMULA   WHEREIN X is alkali metal or hydrogen.

United States Patent [191 Harken et al.

[ 3-HYDROXY-P-DIOXANE-2-METHANOL [75] Inventors: Russell D. Harken, Maryland Heights; F. Wyman Morgan, Ballwin, both of Mo.

[73] Assignee: Monsanto Company, St. Louis, Mo.

[22] Filed: Mar. 18, 1974 [21] Appl. No.: 452,309

[52] US. Cl 260/340.6; 260/484 P; 260/535 P [51] Int. Cl C07d 15/12 [58] Field of Search 260/3406 [56] References Cited UNITED STATES PATENTS 2,331,993 10/1943 MacDowell et a1 260/3406 2,356,683 8/1944 Mikeska et al. 260/3403 2,418,297 4/1947 French et a1 260/3406 2,434,414 l/l948 Kharasch 260/3406 3,433,806 3/1969 Cavitt 260/3406 FOREIGN PATENTS OR APPLICATIONS 745,979 5/1933 France 260/3406 749,713 5/1956 United Kingdom 260/3406 OTHER PUBLICATIONS Chemical Abstracts, Vol. 58, 9054a, (1963). Chemical Abstracts, Vol. 65, l71l3g, (1966). Chemical Abstracts, Vol. 79, l8729k, (1973). Chemical Abstracts, Vol. 79, 7170v, (1973).

[ June 10, 1975 Abstract of German Offen. 2,248,708, April 12, 1973.

[57] ABSTRACT A novel compound represented by the formula CH CHCI-I OH 2 I 2 CH CHOH is useful as an intermediate for preparation of sequestrant compounds represented by the formula COOX COOX CH O CH COOX wherein X is alkali metal or hydrogen.

1 Claim, No Drawings 1 3-HYDROXY-P-DIOXANE-2-METHANOL BACKGROUND OF THE INVENTION This invention relates to a novel compound useful as an intermediate for making ether tricarboxylates represented by the formula coox COOX a CH O CH COOX SUMMARY OF THE INVENTION This invention provides a novel intermediate for preparation of the above-described ether tricarboxylates which intermediate is a compound represented by the formula o CH CHCH OH CH CHOH This compound, its preparation, and use will be understood from the following description of the preferred embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The compound of this invention is 2-hydroxy-3- hydroxymethyl-l ,4-dioxane CI:I CH-OH CH H-CH OH The 2-hydroxy-3-hydroxymethyl-l,4-dioxane can be prepared by a Prins reaction wherein formaldehyde is reacted with p-dioxene (a known compound whose synthesis is described by Moss and Paige, J. Eng. Chem. Data, 12, 452 (1967). In this reaction, acid e.g., sulfuric acid, is added to formaldehyde and p-dioxene combined with the mixture. The acid catalyst can then be neutralized, e.g., with sodium carbonate, and water removed by evaporation to leave the desired product. Preferably the temperature of the reaction is maintained below 40C. The amount of acid catalyst used for given reaction conditions can be optimized by routine tests. Generally, increasing catalyst concentration increases by-product formation whereas decreasing the concentration lowers the reaction rate.

The Z-hydroxy-3-hydroxymethyl-l,4-dioxane can be oxidized to yield COOX COOX CH O CH COOX For example, the oxidation can be accomplished using CrO preferably dissolved in H as an oxidizing agent. This reaction yields the ether tricarboxylic acid which can be esterified by conventional procedures to facilitate isolation of the ester by conventional solvent extraction procedures, e.g., with chloroform. The ester form of the ether tricarboxylate is readily converted to the salt form by reaction with alkali metal hydroxide.

Oxidation conducted under basic conditions will" yield the salt forms of the ether tricarboxylate directly.

The invention is further illustrated by the following example wherein all parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 About 129 grams p-dioxene is added slowly to a mixture of 2.7 grams sulfuric acid and 130 grams 37 percent formalin (a solution of formaldehyde in water).'

During addition the mixture is maintained below 40C. The mixture is stirred for about 14 hours and then neutralized to pH 7 with saturated Na CO solution. The solution is concentrated by evaporation of water and filtered to separate Na SO About 2 grams of the resulting 2-hydr0xy-3- hydroxymethyl-l ,4-dioxane is dissolved in 3 grams water and added to a mixture of 7.5 grams CrO 22 grams H2804 and 33.7 grams H O cooled to 0C. Exothermic oxidation is complete in a few minutes yielding COOH COOI-I CH O CH I COOH The chloroform is evaporated and the ester is converted to COONa COONa Eu o ca COONa by reaction with sodium hydroxide.

What is claimed is: 1. A compound represented by the formula CHOH 

1. A COMPOUND REPRESENTED BY THE FORMULA 